KR100226142B1 - Benzophenone derivatives, UV absorbers and external skin preparations containing them - Google Patents

Abstract

The present invention relates to a benzophenone derivative represented by the following general formula (1),

In said General formula (1), A is a residue remove | excluding one hydroxyl group from sugar or sugar alcohol, B represents the benzophenone group shown by following General formula (2).

(Wherein R ₁ , R ₂ are hydrogen or hydroxyl groups R ₃ to R ₁₀ are hydrogen or hydroxyl groups, alkoxy groups or the above-mentioned binder C and at least one is binder C).

In the case of an alkoxy group, preferred is 1 to 4 carbon atoms, C is -OR- (O is oxygen, R represents an aliphatic chain, preferably 1 to 4 carbon atoms) or 1 mole of glycerin, and one hydroxyl group Combine A with the other hydroxyl with B.)

According to the benzophenone derivative according to the present invention, it has excellent ultraviolet absorbing ability and polar solvent compatibility, and the external preparation for skin can be blended with the polar base and can exhibit excellent usability.

Description

Benzophenone derivatives, UV absorbers and external skin preparations containing them

1 is an infrared absorption spectral chart of 1- (4-benzoylphenyl) glycerolmultitoluether related to one embodiment of the present invention.

2 is a ¹³ C-NMR spectrum chart of 1- (4-benzoylphenyl) glycerolmultitoluether related to one embodiment of the present invention.

3 is a ¹ H-NMR spectrum chart of 1- (4-benzoylphenyl) glycerol multitoluether according to one embodiment of the present invention.

4 is an ultraviolet absorption spectrum chart of 1- (4-benzoylphenyl) glycerol multitoluether according to one embodiment of the present invention.

5 is an infrared absorption spectrum chart of 1- (4-benzoyl-3-hydroxyphenyl) glycerol multitoluether related to one embodiment of the present invention.

6 is a ¹³ C-NMR spectrum chart of 1- (4-benzoyl-3-hydroxyphenyl) glycerolmultitoluether related to one embodiment of the present invention.

7 is a ¹ H-NMR spectrum chart of 1- (4-benzoyl-3-hydroxyphenyl) glycerol multitoluether according to one embodiment of the present invention.

8 is an ultraviolet absorption spectrum chart of 1- (4-benzoyl-3-hydroxyphenyl) glycerol multitoluether according to one embodiment of the present invention.

9 is an infrared absorption spectrum chart of 2-hydroxy4- (2-maltosyloxyethoxy) benzophenone according to one embodiment of the present invention.

10 is a ¹³ C-NMR spectrum chart of 2-hydroxy4- (2-maltosyloxyethoxy) benzophenone according to one embodiment of the present invention.

FIG. 11 is a ¹ H-NMR spectrum chart of 2-hydroxy4- (2-maltosyloxyethoxy) benzophenone according to one embodiment of the present invention. FIG.

12 is an ultraviolet absorption spectrum chart of 2-hydroxy4- (2-maltosyloxyethoxy) benzophenone according to one embodiment of the present invention.

13 is an infrared absorption spectrum chart of 2-hydroxy4- (2-glucosyloxyethoxy) benzophenone according to one embodiment of the present invention.

14 is a ¹³ C-NMR spectrum chart of 2-hydroxy4- (2-glucosyloxyethoxy) benzophenone according to one embodiment of the present invention.

Fig. 15 is a ¹ H-NMR spectrum chart of 2-hydroxy4- (2-glucosyloxyethoxy) benzophenone according to one embodiment of the present invention.

FIG. 16 is an ultraviolet absorption spectrum chart of 2-hydroxy4- (2-glucosyloxyethoxy) benzophenone according to one embodiment of the present invention. FIG.

17 is an infrared absorption spectrum chart of 2-hydroxy4- (2-maltosyloxypropyloxy) benzophenone according to one embodiment of the present invention.

FIG. 18 is a ¹³ C-NMR spectrum chart of 3-hydroxy4- (2-maltosyloxypropyloxy) benzophenone according to one embodiment of the present invention. FIG.

Fig. 19 is a ¹ H-NMR spectrum chart of 3-hydroxy4- (2-maltosyloxypropyloxy) benzophenone according to one embodiment of the present invention.

20 is an ultraviolet absorption spectral chart of 3-hydroxy4- (2-glucosyloxypropyloxy) benzophenone according to one embodiment of the present invention.

The present invention relates to a benzophenone derivative, an ultraviolet absorber and an external preparation for skin, and more particularly, to a benzophenone derivative having high solubility in aqueous phase, an ultraviolet absorber and an external preparation for skin using the same.

Usually, most of the ultraviolet rays received by the human body are derived from sunlight.

Ultraviolet rays contained in sunlight are dermatologically long-wavelength ultraviolet rays (UV-A) of 400 nm to 320 nm, medium-wavelength ultraviolet rays (UV-B) of 320 nm to 290 nm, and short wavelength ultraviolet rays of 290 nm or less (UV-C). Are classified as).

Among them, ultraviolet rays having a wavelength below 290 nm are absorbed by the ozone layer and do not reach the surface.

Ultraviolet rays that reach the surface have several effects on human skin.

Among the ultraviolet rays reached to the ground, UV-A causes browning of the skin and promotes the decrease of elasticity of the skin and the occurrence of wrinkles, leading to rapid aging.

It also promotes the onset of erythema reactions and, in some types of patients, increases the response, which may be the cause of more phototoxic or allergic reactions.

On the other hand, UV-B also causes erythema or blisters on the skin, melanin formation is enhanced, and pigmentation occurs.

For this reason, it is possible to prevent the aging of the skin and to prevent the occurrence and adverse effects of blemishes and freckles, and to protect the skin from ultraviolet rays, various ultraviolet absorbers have been developed.

As a conventional ultraviolet absorber, PABA derivatives, cinnamic acid derivatives, salicylic acid derivatives, benzophenone derivatives, urocanine derivatives, camphor derivatives and heterocyclic derivatives have been used.

These ultraviolet absorbers have been commonly formulated into external skin preparations such as cosmetics or quasi-drugs, but low molecular weight dimethylsiloxane bases are widely used in external preparations.

In other words, the most frequent use of sunscreen cosmetics in summer is the oil-based base in terms of cold resistance, water resistance, etc. As a result, it has been mostly useful as a UV absorber.

Recently, however, there has been a problem in the influence of ultraviolet rays received in daily life, and sunscreen cosmetics are also required in normal skin care.

Therefore, it can be blended in a large amount in skin care products such as water lotion, and it is better to mix a large amount of UV absorber to the whole even when prescribing an external agent having higher UV absorption effect. Since it is preferable to mix | blend an absorber, the development of the substance which absorbs ultraviolet-ray by water solubility is calculated | required greatly.

As described above, most of the conventional ultraviolet absorbers have low water solubility due to their usefulness and limited prescription.

As the water-soluble ultraviolet absorber, only 2-hydroxy-4-methoxy-5-suloxoniumbenzophenone sodium salt is known, and since it is a salt, there has been a problem affecting the pH of the prescription system.

This invention is made | formed in view of the subject of the said prior art, The objective is to provide the substance which has the outstanding ultraviolet absorption, water-soluble, and the skin external preparation which mix | blended it.

As a result of careful examination by the present inventors in order to achieve the said objective, they discovered that a benzophenone derivative has the outstanding ultraviolet absorption and polar solvent compatibility, and came to complete this invention.

That is, the benzophenone derivative of Claim 1 of this applicant is represented by following General formula (1).

(In the general formula (1), A is a residue obtained by removing one or more hydroxyl groups from a sugar or sugar alcohol, B is a benzophenone group represented by the following general formula (2),

(In the general formula (2), R ₁ ~R ₁₀ denotes hydrogen or a hydroxyl group, or alkoxy group or a binder C of the C ₁ ~C _4, is a dog binder C)

C corresponds to -ORO- (O is oxygen, R is C _1-4 fatty chain), or 1 mole of glycerin, of which one hydroxyl group is bonded to A and the other hydroxyl group to B, and n is 1 Is an integer greater than or equal to

The ultraviolet absorber of Claim 2 is characterized by including 1 type (s) or 2 or more types of benzophenone derivatives of the said General formula (1).

The external preparation for skin according to claim 3 is characterized by comprising one or two or more benzophenone derivatives of the general formula (1).

In addition, the benzophenone derivative of Claim 4 of this application is represented by following General formula (3).

(In the formula (3), A is a residue obtained by removing one or more hydroxyl groups from a sugar or sugar alcohol, C is equivalent to 1 mole of glycerin, and one of the hydroxyl groups is bonded to A and the other hydroxyl group to B, B is a benzophenone group represented by the following general formula (4),

(In the general formula (4), one of R ₁ to R ₉ is C, and the other is hydrogen or a hydroxyl group, an alkyl group, an alkoxyl group.)

n is an integer greater than or equal to 1)

The ultraviolet absorber of Claim 5 is characterized by including 1 type (s) or 2 or more types of benzophenone derivatives of the said General formula (3).

The skin external preparation according to claim 6 is characterized in that it contains one or two or more benzophenone derivatives of the general formula (3).

In Formula (3), A is a residue of sugar or sugar alcohol, and specific examples of sugar include glucose, galactose, xylose, fructose, altorose, talos, mannose, arabinose, idose, rickisose, ribose and allose. Monosaccharides and mixtures thereof, or maltose, isomaltose, lactose, xylobiose, kenthiobiose, cordiobis, cellobiose, sohorose, nigerose, sucrose, merribiose, laminaribiose, lutinos It is also possible to use disaccharides such as disaccharides and mixtures thereof, or trisaccharides such as maltotriose and mixtures thereof, or more polysaccharides and mixtures thereof, and also monosaccharides thereof, and polysaccharide mixtures thereof. Specific examples of the sugar alcohols include sugar alcohols such as multitol, sorbitol, mannitol, garicuccitol, glycitol, inositol, multitriol, and mixtures thereof, or polysaccharide alcohols and mixtures thereof, or mixtures of sugar alcohols thereof. Can be.

The same effect can also be obtained by using a mixture of these monosaccharides, disaccharides, trisaccharides and more polysaccharides and sugar alcohols.

In General Formula (4) representing the benzophenone group B, R ₁ to R ₄ represent hydrogen or a hydroxyl group, an alkyl group or an alkoxyl group, or a bonding group with C.

In the case of an alkyl group or an alkoxyl group, the fatty chain may be a straight chain alkyl group, a branched alkyl group, an unsaturated alkyl group or a cycloalkyl group. Specific examples of the aliphatic chain include a methyl group, an ethyl group, an acetylenyl group, a propyl group, an isopropyl group, a propenyl group and a butyl group. , Isobutyl group, t-butyl group, butenyl group and the like.

Although there is no significant difference in the ultraviolet absorption wavelength in all, methyl group and ethyl group are preferable especially from industrial viewpoint.

C is a glycerin group which is equivalent to 1 mole of glycerin, regardless of any bonding portion.

n represents an integer and 1 to 3 are preferable in terms of water solubility.

Since the benzophenone derivative is extremely safe and stable in a solid or syrup state, the benzophenone derivative can be blended with chemicals such as dyes, inks, plastics, coatings, and chemical fibers, and as a component of pharmaceuticals, quasi-drugs, cosmetics, and cleaning agents. Can be combined.

In addition, there is a property of having moisture retention.

The benzophenone derivatives of the general formula (3) are glycidylated hydroxybenzophenones represented by the general formula (5), and the glycidyloxybenzophenones represented by the general formula (6) are obtained by sugar, sugar alcohol and special elements. It can manufacture by reacting by the method of 61-180989.

For example, it can synthesize as follows.

As the compound represented by the general formula (6), the compound represented by the general formula (5) may be obtained by the method of Sandra et al. {SRSandler, FRBerg.J.Appl.Polymer.Soc. 9,3707 (1965)} and the method of Lobart. It can synthesize | combine by making it react by {Tetrhedorn, 35,2169-2172 (1979)}.

That is, it is dissolved or suspended in non-aqueous solvents such as dimethyl sulfoxide, dimethylformamide, diocylic acid, dimethylacetamide, N-methylpyrrolidone, N-acetylmorpholine, and N-methyl amber acid amide, or dissolved in an acetone aqueous solvent. Suspended or stirred with epichlorohydrin at 90-130 ° C. under a catalyst with no solvent, and the reaction may be carried out under a stream of nitrogen or argon, or the compound represented by the general formula (5) alone or in combination of two or more thereof. good.

The catalyst used at this time is a Lewis acid catalyst such as BF ₃ · Et ₂ O, aluminum trioxide, P-toluenesulfonic acid, heteropolyphosphoric acid, hydrochloric acid, acid catalysts such as sulfuric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydroxide, Amine, such as alkali, such as sodium alcoholate, and N-methylbenzylamine, etc. are mentioned.

The compound shown by General formula (3) can be manufactured by the method etc. which make the compound shown by General formula (4) obtained by reaction with sugar, a sugar alcohol, the method of No. 61-180989, etc. are mentioned.

For example, it can synthesize | combine by the following method.

Sugars and sugar alcohols are dissolved or suspended in non-aqueous solvents such as dimethylsulfoxide, dimethylformamide, dioxic acid, dimethylacetamide, N-methylpyrrolidone, N-acetylmorpholine, and N-methyl zucchinamide. It stirred at 90-130 degreeC under the compound and catalyst which were shown in 6), At this time, reaction may be used under airflow, such as nitrogen and argon, and the compound shown by General formula (6) may be used individually or in combination of 2 or more types.

The catalyst used at this time is acid catalysts such as p-toluenesulfonic acid, heteropolyphosphoric acid, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydroxide, salts such as sodium alcohol, salts such as ammonium chloride and sodium chloride And amines such as N-methylbenzylamine.

As for the molar ratio of the sugar and sugar alcohol used for this reaction, and the compound shown in General formula (6), for example, when it is going to obtain monoether as a main product, 1: 1-3: 1 are preferable, and 2: 1-3 : 1 is more preferable.

When the molar ratio of sugars and sugar alcohols to the compound represented by the general formula (6) is out of this range, that is, if the sugar and sugar alcohols are small, impurities such as tetraether are likely to be generated. It is not preferable because it causes trouble.

When acids and alkalis are used as catalysts, after all of the compounds represented by the general formula (6) are consumed, an acid such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkalis such as sodium hydroxide and potassium hydroxide is added for the purpose of neutralizing the catalyst of the reaction system. did.

After these reactions, the reaction solvent may be distilled off under reduced pressure and the product may be used as it is, or may be distributed in a solvent or the like, or may be purified by column chromatography or recrystallization.

In the reaction product thus obtained, in addition to the benzophenone derivative represented by the general formula (3), n or more compounds, salts, unreacted sugars and sugar alcohols in the general formula (3) coexist.

Thus, for example, when sugars, sugar alcohols, and salts are removed, they are extracted with a solvent such as methyl alcohol, ethyl alcohol, butyl alcohol, isopropyl alcohol, or partitioned into water containing a large amount of salt, methyl ethyl ketone, n-butanol, and the like. It can refine | purify by separating an organic solvent layer.

In addition, when the sugar, sugar alcohol and salt are removed and the compound is separated, the reaction product is suspended in water or a mixture of water and alcohol, and hyperplus polymer (for example, Hiplus resin manufactured by Mitsumi Chemical Co., Ltd.), octadecyl It can be purified by separating the liquid by first passing it through water with a reverse phase-distributing column such as silica and then passing it through a mixture of alcohol, such as methanol and ethanol, polar organic solvent such as acetonitrile and water.

Furthermore, after removing a salt etc., pure phase systems, such as a silica gel column chromatography method, can be refine | purified.

As the water-soluble ultraviolet absorber, a water-soluble ultraviolet absorber incorporating a nonionic hydrophilic group is preferable by reducing the effect on the pH of the system.

As a nonionic hydrophilic group, mainly polyethylene oxide, polyglycerol, a sugar, etc. can be obtained.

Among them, polyethylene oxide has been considered to be unfavorable in terms of stability recently, in that it contains dioxane such as decomposing over time and generating formarin.

From this point of view, polyglycerol and sugar with high safety are preferred. On the other hand, although the base is required to be a single component, polyethylene oxide and polyglycerol tend to be a mixture having a distribution of added water due to the nature of the synthesis reaction, and for this reason, purification is not easy.

On the other hand, a hydrophilic group such as sugar may be preferable in that the product is less likely to be a mixture and the purification is easy.

However, there is a problem in that when a reaction such as etherification or esterification is performed directly on sugars, it becomes a mixture due to the difference in the number of added moles.

Thus, the present inventors have developed the following benzophenone derivatives to solve this problem.

That is, the benzophenone derivative of Claim 7 of this invention is represented by following General formula (7).

(In general formula (7), R <_1> , R <_2> is hydrogen or a hydroxyl group, one or more is a hydroxyl group, R <_3> -R <_10> is represented by hydrogen or a hydroxyl group, or the C _1-4 alkoxy group or -OROA. , One is represented by -OROA, A is a residue from which one hydroxyl group is removed from sugar, R is C _1-4 fatty chain)

The ultraviolet absorbent of Claim 8 contains 1 type, or 2 or more types of the benzophenone derivatives of the said General formula (7).

The skin external preparation of Claim 9 contains 1 type, or 2 or more types of the benzophenone derivatives of the said General formula (7).

In Formula (7), A is a residue of a sugar, and specific examples of the sugar include monosaccharides such as glucose, galactose, xylose, fructose, altorose, talos, mannose, arabinose, idos, rickissos, ribose, and aros. And mixtures thereof, or disaccharides such as maltose, isomaltose, lactose, xylobiose, kenthiobis, cordiobis, cellobiose, sohorose, nigerose, sucrose, meribios, laminaribiose, and lutinos. And mixtures thereof, or trisaccharides such as maltotriose, and mixtures thereof, and further polysaccharides and mixtures thereof, and also mixtures of monosaccharides, disaccharides and more thereof.

In R ₃ to R ₁₀ , in the case of using OROA, the aliphatic chain to be R may be a straight chain alkyl group, a branched alkyl group, an unsaturated alkyl group or a cycloalkyl group. Specific examples of the aliphatic chain include a methyl group, an ethyl group, an acetylenyl group, a propyl group, Isopropyl group, propenyl group, butyl group, isobutyl group, t-butyl group, butenyl group and the like.

Although there is no remarkable difference in the ultraviolet absorption wavelength in all, methyl group and ethyl group are preferable especially in industrial use.

In the case of using an alkoxy group in R ₃ to R ₁₀ , any of an aliphatic chain or a linear alkoxy group, a branched alkoxy group, an unsaturated alkoxy group or a cycloalkoxy group of the alkoxy group may be used, and specifically, a methoxy group, an ethoxy group and an acetylenyl jade. A time period, a propyloxy group, an isopropyloxy group, a propenyloxy group, a butyloxy group, an isobutyloxy group, t-butyloxy group, butenyloxy group, etc. are mentioned.

Although there is no noticeable chain in ultraviolet absorption wavelength in all, a methoxy group and an ethoxy group are especially preferable in water solubility etc. and industrial uses.

Since the benzophenylphenone derivative is solid and has excellent safety and stability, it can be blended with chemicals such as paints, inks, plastic coating agents, and chemical fibers, and can be blended as a component of pharmaceuticals, cosmetics, and cleaning agents. have. The benzophenol derivatives related to the general formula (7) can be synthesized using, for example, a saccharide-modified lysis catalyst described in Japanese Patent Application Laid-Open No. 63-84637, and are generally used for glycosylation (Kenic Schenkol Reaction, Hepereihi). Method or other ether exchange method) may be used.

For example, it can synthesize as follows.

The acetylide of sugar is made into nonpolar solvent such as dibufilcellosolve, toluene, or without solvent (8)

(Wherein R ₁ and R ₂ are the same as in the electrochemical chamber (2), and R ₃ to R ₁₀ may be represented by hydrogen, a hydroxyl group, an alkoxy group or OR-OH and at least one may be represented by OR-OH.) Preferably, the compound having 1 to 4 carbon atoms and R represents an aliphatic chain, preferably 1 to 4 carbon atoms is added, and the mixture is stirred at 90 to 130 ° C. in the presence of an acid catalyst, and the reaction is carried out under reduced pressure. The compound shown by () may be used alone or in combination of two or more.

Examples of the catalyst used at this time include p-toluenesulfonic acid, heteropolyphosphoric acid, zinc acetate, zinc chloride or ion exchange resins.

After the reaction, the reaction solvent is distilled off under reduced pressure, and the product is extracted with toluene and washed with water.

The obtained effluent is deacetylated as it is after concentration under reduced pressure. After purification by silica gel column chromatography, deacetylation may be performed.

In the reaction product thus obtained, salts and sugars during neutralization coexist in addition to the benzophenone derivatives represented by the general formula (7).

Thus, for example, to remove sugars and salts, extract with a solvent that does not dissolve sugars such as methyl alcohol, ethyl alcohol, butyl alcohol and isopropyl alcohol, or water containing a large amount of salt, methyl ethyl kenone and n-butanol. It can divide and refine | purify by separating an organic solvent layer.

In addition, when benzophenone derivatives are separated by removing sugars and salts, the reaction product is suspended in water or a mixture of water and alcohol, and a hyperplus polymer (for example, a high plus resin manufactured by Mitsubishi Chemical Corporation) octadecyl silica, etc. It can be produced by separating the liquid by first passing it through water as a reverse phase distribution column and then passing it through a mixture of alcohols such as methanol and ethanol, polar organic solvents such as acetonitrile and water.

The above-described benzophenone derivative may be used after distilling off the extraction solvent or purifying by column.

The benzophenone derivative thus obtained is excellent in chemical stability, oxidation stability, water solubility, absorbed in the ultraviolet region, and excellent in moisture retention.

Since the benzophenone derivative of this invention is excellent in safety, it can be mix | blended with cosmetics, a pharmaceutical material, etc.

In addition to the present invention, cosmetic materials and medical material components other than those commonly used can be appropriately blended.

For example, various hydrocarbons, fats and oils, such as liquid paraffin, squalene, petrolatum, cetyl alcohol, isosateyl alcohol, 2-ethylhexanoate cetyl, 2-octyldodecyl alcohol, triisostearic acid glycerin, macadamian nut oil and lanolin, Oily ingredients such as Rowe, silicones, surfactants, thickeners, neutralizers, preservatives, fungicides, antioxidants, powder components, pigments, flavorings and other ultraviolet absorbers, drugs, metal blockers, pH preparations, and the like. .

EXAMPLE

Examples of the present invention are shown below, but this does not limit the technical scope of the present invention.

The compounding amount is weight%.

Example 1

1- (4-benzoylphenyl) glycerol multitoluether

After dissolving 1 g of 4-hydroxybenzophenone and 4.668 g (0.025 mol) of epichlorohydrin, 20.54 mg of sodium hydroxide was added, the reaction system was heated to 100 °, and 201.4 mg of sodium hydroxide was added thereto at 95 ° C., followed by heating and stirring. Was carried out for 3 hours.

After cooling the system to room temperature, the salt was filtered off.

The obtained filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 1.0 g (yield 83%) of 4-glycidyloxybenzophenone as a solid.

Next, a solution in which 921 mg of 4-glycidyloxybenzophenone was dissolved in 1 ml of dimethyl sulfoxide was dissolved by dissolving 2.921 g of multitol and 476.0 mg of potassium hydroxide in 20 ml of dimethyl sulfoxide, followed by heating and stirring for 30 minutes under a nitrogen stream. Dropped.

The mixture was further stirred for 1 hour under a nitrogen stream, cooled to room temperature and neutralized with hydrochloric acid.

The reaction system was partitioned using a column chromatography method of a hyperpolar polymer (Hipolar resin made by Mitsubishi Chemical Co., Ltd.) as a developing solvent, first using purified water, followed by methyl alcohol: purified water = 1: 1, and then ethyl alcohol: Purified water = 1: 1 The eluate was concentrated to obtain 500 mg (absorption rate 30%) of 1- (4-benzoylphenyl) glycerol multitoluether.

(1) Infrared absorption spectrometry.

As measured by KBR method using IRA-1 infrared absorption spectrum measuring device manufactured by Nippon Kagaku Kogyo Co., Ltd., the expansion vibration of hydroxyl group is 3387 cm ^-1 , the expansion vibration of glycerol group is 2928cm ^-1 , and 1649 cm ^-1. Absorption by stretching of the carbonyl group was observed.

The results are shown in FIG.

(2) ¹³ C-NMR Measurement

JOEL GX-400 manufactured by Nippon Electronics Co., Ltd. measured CD ₃ OD at 35 ° C. as a solvent, and the signal derived from carbon of the benzophenone portion was δ197ppm, 164ppm, 139ppm, 134ppm, 133ppm, 131ppm, 129ppm, 115ppm. Signals derived from the multitol group and the gglyceryl group were observed at ˜62 ppm, respectively.

The results are shown in FIG.

(3) ¹ H-NMR measurement

JOEL GX-400 manufactured by Nippon Electronics Co., Ltd. measured CD ₃ OD at room temperature as a solvent. As a result, a signal derived from hydrogen of the benzophenone moiety was δ5.2 ppm to 3.3 ppm at δ7.8 ppm to 7.1 ppm. The signals derived from hydrogen of the glyceryl group were observed, respectively.

The results are shown in FIG.

(4) UV absorption spectrum measurement method

Nippon Spectroscopy Industry Co., Ltd. UVIDEC 61OC UV absorption spectrum measurement device was commercially available and measured by solvent methanol showed maximum absorption at 282.7nm.

The results are shown in FIG.

(5) Phenolic Reagents

Spotting on the product JLC and dispensing the phenol indicators with a nebulizer followed by spraying with a 10% aqueous sodium hydrogen carbonate solution did not give a color when phenol was present.

Example 2

1- (4-benzoyl-3-hydroxyphenyl) glycerolmultitoluether

2,4-hydroxybenzophenone 3.0g and epichlorohydrin 15.55g (0.075mol) were dissolved, and sodium hydroxide 112.0 mg was added.The reaction system was heated to 100 ° and sodium hydroxide 672.2 mg was added. On the other hand, heat stirring was performed for 3 hours.

After cooling the system to room temperature, the salt was filtered off.

The obtained filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 2.8216 g (yield 75%) of solid 4-glycidyloxy-2-hydroxybenzophenone.

Next, 1.550 g of multitol and 84.2 mg of potassium hydroxide were dissolved in 10 ml of dimethyl sulfoxide and heated and stirred for 30 minutes under a stream of nitrogen to obtain 406.0 mg of 4-glycidyloxy-2-hydroxybenzophenone obtained by dimethyl sulfoxide 6 The solution dissolved in mL was dropped.

The mixture was further stirred for 1 hour under a nitrogen stream, cooled to room temperature and neutralized with hydrochloric acid.

The reaction system was partitioned using a column chromatography method of a hyperpolar polymer (Hipolar resin made by Mitsubishi Chemical Co., Ltd.) as a developing solvent, first using purified water, followed by methyl alcohol: purified water = 1: 1, and then ethyl alcohol: Purified water = 1: 1 The eluate was concentrated to give 478 mg (absorption rate: 52%) of 1- (4-benzoyl-3hydroxyphenyl) glycerol multitoluether.

(1) Infrared absorption spectrum measurement method.

Japanese minutes Mining Co., Ltd., IRA-1 using infrared absorption spectrum measuring apparatus, and the stretching vibration of the hydrocarbon group in the stretching vibration, 2928㎝ ^-1 of the hydroxyl group in the resulting 3380㎝ ^-1 as measured by a KBr tablet method, 1626㎝ ^-1 Absorption by stretching of the carbonyl group was observed.

The results are shown in FIG.

(2) ¹³ C-NMR Measurement

JOEL GX-400 manufactured by Nippon Electronics Co., Ltd. measured the CD ₃ OD at 35 ° C. as a solvent. At 109 ppm to 62 ppm, signals derived from the multitol group and the glyceryl group were observed, respectively.

The results are shown in FIG.

(3) ¹ H-NMR measurement

JOEL GX-400 manufactured by Nippon Electronics Co., Ltd. measured CD ₃ OD at room temperature as a solvent. The signal derived from hydrogen of the benzophenone moiety was δ5.2 ppm to 3.3 ppm at δ12.5 ppm and 7.8 to 7.1 ppm. Signals derived from hydrogen of the tall group and the glyceryl group were observed, respectively.

The results are shown in FIG.

(4) UV absorption spectrum measurement method

Japan Spectrophotometer Co., Ltd. UVIDEC 61OC Ultraviolet absorption spectrum measuring apparatus was used and measured with solvent methanol, and shows the maximum absorption at 279.8 nm.

The results are shown in FIG.

(5) Phenolic Reagents

After spotting the main substance on JLC and dispensing the phenolic indicator with an atomizer, spraying 10% aqueous sodium hydrogen carbonate solution did not show the color when phenol was present.

Example 3

4,4'- multi hydroxy glyceroxy -2,2 'hydroxy benzophenone

After dissolving 3.0 g of 2,2 ', 4,4'-tetrahydroxybenzophenone and 31.1 g (0.075 mol) of epichlorohydrin, 2240.0 mg of sodium hydroxide was added thereto, and the reaction system was heated up to 100 ° C. and then set at 95 ° C. Sodium was added and heat stirring was performed for 3 hours.

After cooling the system to room temperature, the salt was filtered off.

The obtained filtrate was concentrated under reduced pressure and purified by silica gel column chromatography to obtain 3.21 g of 4 Pa, 4-diglycidyloxy-2,2'-hydroxybenzophenone as a solid.

Next, 4'4, -diglycidyloxy-2,2'-dihydroxy obtained by dissolving 1.550 g of multitol and 84.2 mg of potassium hydroxide in 10 ml of dimeltyl sulfoxide and heating and stirring for 30 minutes under a nitrogen stream. The solution which melt | dissolved 606.0 mg of benzophenone in 7 ml of dimethyl sulfoxide was dropped.

The mixture was further stirred for 1 hour under a nitrogen stream, cooled to room temperature, and neutralized with hydrochloric acid.

The reaction was first divided into purified solvent and then using ether alcohol: purified water = 1: 1 as a developing solvent by the column chromatograph method of the hyperpolar polymer (Hyperpolar resin made by Mitsubishi Chemical Industries, Ltd.) and ether alcohol: purified water. = 1: 1 The elution part was concentrated and 780 mg of 4,4'- multi hydroxy glyceroxy-2,2'- hydroxy benzophenone was obtained.

[Test Example 1]

Preparation of Serum

In the formulation shown in Table 1, a cosmetic solution containing a benzophenone derivative was prepared, and a cosmetic solution containing 2-hydroxy-4-methoxy-5-sulfonium benzophenone as a control example was prepared.

TABLE 1

Alcohol phase A was added to the aqueous phase B to solubilize the perfume to obtain a cosmetic liquid.

The compounding example 1 was colorless, transparent and viscous, and the favorable cosmetic liquid was obtained, whereas the comparative example 1 was a strong yellowish tinge and no viscosity.

[Test Example 2]

UV light blocking test

Two essences prepared in Test Example 1 were used and tested directly on the beach.

As a method, the sample was apply | coated to the tummy of 20 men and women, and the degree of sunburn was determined.

Evaluation standard of sunlight degree of sunlight

A dark red face was recognized ...

A little dark red face was recognized ...

Red face could not be recognized

The results are shown in Table 2.

TABLE 2

From these results, the skin external preparation containing the benzophenone derivative was higher in the UV protective effect and safer than the skin external preparation incorporating the conventional water-soluble ultraviolet absorbent.

[Test Example 3]

Moisturizing

The skin conduction change of 15 men and women was measured in an environment of 25 ° C. and 50% relative humidity.

The cosmetic liquid prepared in Test Example 1 was applied to the shoulder portion, and skin conduction of the shoulder portion after 24 hours after the treatment was measured and judged at the increase rate.

Conductivity increase rate = increase in conduction value / conduction value before treatment

15% increase in conduction rate

Conduction growth rate 15% or more but less than 30%

More than 30% increase in conduction rate

The results are shown in Table 3.

TABLE 3

From the above results, it has been found that the external skin preparations incorporating the benzophenone derivative according to the present invention have superior moisturizing properties than the external skin preparations incorporating a water-soluble ultraviolet absorbent.

Example 4

2-hydroxy4- (2-maltosyloxyethoxy) benzophenone

1 g of 2,4-dihydroxybenzophenones were dissolved by adding 7 g of ethyl bromerhydrin, 37 mg of sodium hydroxide, and 0.25 g of purified water.

After stirring and heating to 100 ° C., the mixture was lowered to 90 ° C. and 224 mg of sodium hydroxide was added thereto.

After 2 hours of heating stirring, the mixture was cooled, extracted with chloroform, washed with water, dried and concentrated.

Purification was performed using a silica gel column chromatography method (toluene: methyl ethyl ketone) to obtain 1.1 g of 2-hydroxy4- (2-hydroxyethoxy) benzophenone.

Subsequently, 100 mg and 1 ml of toluene were dissolved, 219 mg of acetylmaltose and 10 g of molybdenum phosphate were added, followed by heating and stirring at 100 ° C. for 30 minutes.

The reaction system was cooled to room temperature, extracted with toluene, washed once with purified water and washed four times with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.

The residue was purified by silica gel column chromatography (hexane: ethyl acetate) to obtain 110 mg of an acetylate of 2-hydroxy 4- (2-maltosyloxyethoxy) benzophenone.

This 2-hydroxy 4- (2-maltosyloxybenzophenone) dissolves 100 mg of an acetylide in 2 ml of methanol, adds 0.3 ml of sodium methylate and stirs at room temperature for 30 minutes, followed by ion exchange resin (e.g. After neutralization with Anbarite IR 120B manufactured by Kano Industrial Co., Ltd. and UBK 530 manufactured by Mitsubishi Chemical, the resin was filtered off and the reaction solution was concentrated under reduced pressure to obtain 2-hydroxy4- (2-maltosyloxyethoxy) benzophenone. .

The yield was 80 mg.

The obtained 2-hydroxy 4- (2-maltosyloxyethoxy) benzophenone was analyzed by the method of following (1)-(6).

Thus obtained 2-hydroxy4- (2-maltosyloxyethoxy) benzophenone was used as sample 1.

(1) Infrared absorption spectrum measurement method

KBR Purification Method using IRA-1 Infrared Absorption Spectrometer manufactured by Nippon Spectroscopy Co., Ltd. as a result of stretching vibration of hydroxyl group at 3400cm ^-1 , stretching vibration of 2-maltosyloxyethoxy group at 2920cm ^-1 , 1630 Absorption was observed in the stretching motion of the carbonyl group at cm ⁻¹ .

(2) ¹³ C-NMR Measurement

As a result of measuring at room temperature the CD ₃ OD as solvent by Japan JOEL GX-400 of the electronic handwritten companies claim.

δ 201ppm, 167ppm, 167ppm, 140ppm, 136ppm, 133ppm, 130ppm, 129ppm, 115ppm, 108ppm, 105ppm, 103ppm, 103ppm, 81ppm, 78ppm, 77ppm, 75ppm, 75ppm, 75ppm, 74ppm, 74ppm, 72ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm, 69ppm A signal was observed at 62 ppm.

The results are shown in FIG.

(3) ¹ H-NMR measurement

As a result of measuring CD ₃ OD as a solvent at room temperature by JOEL GW-400 manufactured by Nippon Electronics Co., Ltd., signals were observed at δ 7.53 to 7.38, 6.46 to 6.39, and 4.72 to 3.11.

The results are shown in FIG.

(4) UV absorption spectrum measurement method

Using the UVIDEC 610 ultraviolet absorption spectrum measurement apparatus of Guccimoto Spectroscopy Co., Ltd., the maximum absorption was obtained at 287.6 nm and 324.6 nm using solvent methanol.

The results are shown in FIG.

(5) Melting point measuring method

As a result of using a capillary melting point measuring apparatus manufactured by ARTHUR H. THOMS COMPANY, it was dissolved at 92 to 110 ° C, but no clear melting point was shown.

(6) water soluble

It was dissolved in water at least 20% by weight.

Example 5

2-hydroxy4- (2-glucosyloxyethoxy) benzophenone

100 mg of 2-hydroxy4- (2-hydroxyethoxy) benzophenone synthesized in Example 4 was dissolved in 2 ml of toluene, 136 mg of acetylglucose was added, and the temperature was raised to 100 ° C. to obtain 50 mg of molybdate phosphate. After addition, the mixture was extracted with toluene, washed once with purified water and washed four times with saturated brine, and then the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.

The residue was purified by silica gel column chromatography (hexane: ether acetate) to obtain 189 mg of acetylate of 2-hydroxy4- (2-glucosyloxyethoxy) benzophenone.

Dissolve 189 mg of the obtained acetylate of 2-hydroxy4- (2-maltosyloxyethoxy) benzophenone in 6 ml of methanol, add 0.6 ml of sodium methylate, and stir for 30 minutes at room temperature, For example, after neutralizing with ambolite 1R 120B manufactured by organo industry and UBK 530 manufactured by Mitsubishi Chemical, the resin was filtered off and the reaction solution was concentrated under reduced pressure to produce 2-hydroxy4- (2-glucosyloxyethoxy) benzophenol. Got. The obtained 2-hydroxy and -C2-glycosyloxyethoxy) benzophenone was analyzed by the following (1)-(6) method.

(1) Infrared absorption spectrum measurement method

KBR Purification Method using IRA-1 Infrared Absorption Spectrometer manufactured by Nippon Spectroscopy Co., Ltd. as a result of stretching vibration of hydroxyl group at 3400cm ^-1 , stretching vibration of 2-glucosyloxyethoxy group at 2920cm ^-1 , 1630 Absorption was observed in the stretching motion of the carbonyl group at cm ⁻¹ .

(2) ¹³ C-NMR Measurement

As a result of measuring at room temperature the CD ₃ OD as solvent by Japan JOEL GX-400 of the electronic handwritten companies claim.

Signals were observed at δ 201 ppm, 167 ppm, 167 ppm, 140 ppm, 136 ppm, 133 ppm, 130 ppm, 129 ppm, 114 ppm, 109 ppm, 108 ppm, 104 ppm, 103 ppm, 78 ppm, 75 ppm, 72 ppm, 69 ppm, 69 ppm, 62 ppm.

The results are shown in FIG.

(3) ¹ H-NMR measurement

As a result of measuring CD ₃ OD at room temperature with JOEL GX-400 manufactured by Nippon Electronics Co., Ltd., signals were observed at δ 7.53 to 7.38, 6.46 to 6.39, and 4.28 to 3.10.

The results are shown in FIG.

(4) UV absorption spectrum measurement method

Using the UVIDEC 610 ultraviolet absorption spectrum measurement apparatus of Guccimoto Spectroscopy Co., Ltd., the maximum absorption was obtained at 286.9 nm and 324.3 nm using solvent methanol.

The results are shown in FIG.

(5) Melting point measuring method

The hygroscopicity of the compound was high and could not be measured.

(6) solubility

About 10% by weight was dissolved in water.

Example 6

2-hydroxy4- (3-maltosyloxypropyloxy) benzophenone

1 g of 2,4-dihydroxybenzophenone was added, and 7.78 g of 1-buromopropane, 40 mg of sodium hydroxide, and 0.1 ml of purified water were dissolved.

After stirring and heating to 100 ° C., the temperature was lowered to 90 ° C. and 220 mg of sodium hydroxide was added again.

After heating and stirring for 4 hours, the mixture was cooled with air, extracted with glow, dried with water, and concentrated.

Purification was carried out using a silica gel column chromatography method (toluene: methyl ethyl ketone) to obtain 1.01 g (yield 80%) of 2-hydroxy4- (3-hydroxypropyloxy) benzophenone.

Octaacetyl maltose 1.14g was added to 460 mg of obtained 2-hydroxy4- (3-hydroxypropyloxy) benzophenone, and it melt | dissolved in 10 ml of toluene, heated up at 90 degreeC, and the catalytic amount of molybdate phosphoric acid was added.

After heating and stirring for 30 minutes, the mixture was air cooled, extracted with 100 ml of toluene, and washed with saturated sodium bicarbonate water.

After drying and concentrating, the product was purified by silica gel column chromatography (toluene: methyl ethyl ketone) to obtain 880 mg (yield 60%) of acetylate of 2-hydroxy4- (3-maltosyloxypropyloxy) benzophenone. Got it.

Dissolve 880 mg of the obtained acetylate of 2-hydroxy4- (3-maltosyloxypropyloxy) benzophenone in 20 ml of methanol, add sodium methoxide, stir for 30 minutes, neutralize with acidic resin, concentrate after filtration and concentrate. 565 mg (yield 100%) of -hydroxy4- (3-maltosyloxypropyloxy) benzophenone was obtained.

Obtained 2-hydroxy4- (3-maltosyloxypropyloxy) benzophenone was confirmed by the following (1)-(6) method.

(1) Infrared absorption spectrum measurement method

Japan Spectroscopic Co., Ltd. using the IRA-1 infrared absorption spectrum measuring apparatus, and expansion and contraction of the 3-end of tosyl oxy group in the stretching vibration, 2920㎝ ^-1 of the hydroxyl group in the resulting 3400㎝ ^-1 measured by the KBr tablet method exercise, 1630㎝ ^- Absorption was observed in the stretching of the carbonyl group at ¹ .

The results are shown in FIG.

(2) ¹³ C-NMR Measurement

As a result of measuring at room temperature the CD ₃ OD as solvent by Japan JOEL GX-400 of the electronic handwritten companies claim.

δ201ppm, 167ppm, 167ppm, 140ppm, 136ppm, 133ppm, 130ppm, 129ppm, 114ppm, 109ppm, 104ppm, 103ppm, 81ppm, 78ppm, 76ppm, 75ppm, 75ppm, 74ppm, 71ppm, 67ppm, 67ppm, 63ppm, 62ppm, 62ppm, 62ppm Observed.

The results are shown in FIG.

(3) ¹ H-NMR measurement

As a result of measuring CDOD as a solvent at room temperature by JOEL GX-400 manufactured by Nippon Electronics Co., Ltd., signals were observed at δ 7.55 ppm, 7.50 ppm, 7.43 ppm, 6.56 ppm, 6.50 ppm, 6.44 ppm, and 5.22 ppm to 1.9 ppm.

The results are shown in FIG.

(4) UV absorption spectrum measurement method

Using the UVIDEC 610 ultraviolet absorption spectrum measuring apparatus of Guccimoto Spectroscopy Co., Ltd., the maximum absorption was obtained at 289.4 nm and 324.1 nm using solvent methanol.

The results are shown in FIG.

(5) Melting point measuring method

It was measured using a capillary melting point measuring apparatus manufactured by ARTHUR H. THOMS COMPANY, and was dissolved at 77 to 87 ° C, but no clear melting point was shown.

(6) solubility

It was dissolved in water at least 20% by weight.

Experimental Example 4

Preparation of Serum

The cosmetic liquid which mix | blended the benzophenone derivative with the benzophenone derivative | guide_body, and the cosmetic liquid which mix | blended 2-hydroxy-4-methoxy-5-suloxonium benzophenol as a control example were produced by the prescription shown in Table 4.

TABLE 4

Alcohol phase A was added to the water phase B to solubilize the perfume to obtain a cosmetic liquid.

The compounding example 2 was a colorless, transparent and viscous good cosmetic liquid, whereas the comparative example 2 had strong yellowish tinge and no viscosity.

[Test Example 5]

UV light blocking test

Two cosmetic liquids prepared in Test Example 4 were used and tested directly on the beach.

As a method, the sample was apply | coated to the tummy of 20 men and women, and the degree of sunburn was determined.

Judgment criteria were as follows.

Evaluation criteria of the degree of sunburn are the same as in Test Example 2 above.

The results are shown in Table 5.

TABLE 5

From these results, the skin external preparation containing the benzophenol derivative was higher in UV protection effect and safer than the skin external preparation incorporating the conventional water-soluble ultraviolet absorbent.

[Test Example 6]

Moisturizing

The moisture retention was investigated based on the said Test Example 3.

The results are shown in Table 6.

TABLE 6

From the above results, it has been found that the external skin preparations incorporating the benzophenone derivative according to the present invention have superior moisturizing properties than the external skin preparations incorporating a water-soluble ultraviolet absorbent.

Hereinafter, a combination example of the external preparation for skin according to the present invention will be described. Each of the external preparation for skin exhibits excellent ultraviolet protective effect.

Example 7

cream

A. Maintenance

Stearic Acid 10.0

Stearin Alcohol 4.0

Stearic Acid Monoglycerin Ester 8.0

Vitamin E Acetate 0.5

Spices 0.4

Ethylparaben 0.1

Butylparaben 0.1

Propylparaben 0.1

B. Award

Propylene Glycol 8.0

Glycerin 2.0

1- (4-benzoyl-3-hydroxyphenyl) glycerol multitoluether 6.0

Potassium Hydroxide 0.4

Disodium Ethate 0.05

Purified water balance

quite

The oil phase part of A and the water phase part of B are respectively heated to 70 ° C. and completely dissolved.

Phase A is added to phase B and flows down into the emulsifier.

The emulsion was cooled using a heat exchanger to obtain a cream.

Example 8

cream

A. Paid

Cetanol 4.0

Vaseline 7.0

Isopropyl myristate 8.0

Squalane 12.0

Dimethylpolysiloxane 3.0

Stearic Acid Monoglycerin Ester 2.2

POE (20) sorbitan monostearate 0.5

Glycylinic Acid Stearate 0.1

BHT 0.02

Ethylparaben 0.1

Butylparaben 0.1

Propylparaben 0.1

B. Award

1,2-butylene glycol 7.0

Disodium Ethate 0.07

Phenoxyethanol 0.2

L-ascorbic acid phosphate ester magnesium salt 3.0

Polyacrylic acid alkyl ester 1.0

1- (4-benzoylphenyl) glycerol multitoluether 8.0

Purified water balance

quite

A cream was obtained according to Example 7.

Example 9

latex

A. Paid

Oleyl oleate 3.0

Vaseline 7.0

Squalene 5.0

Sorbanthose skioleate ester 0.8

Polyoxyethylene Oleyl Ether 1.2

1- (4-benzoyl-3-hydroxyphenyl) glycerol sorbate ether 3.0

Methylparaben 0.1

Spices 0.12

B. Award

Dipropylene Glycol 5.0

Ethanol 3.0

Carboxy Vinyl Polymer 0.17

Sodium hyaluronate 0.01

Polyacrylic acid alkyl ester 1.0

1- (4-benzoyl-3-hydroxyphenyl) glycerolsugar ether 4.0

Potassium Hydroxide 0.08

Sodium hexametaphosphate 0.05

Purified water balance

quite

The emulsion was obtained in Example 7.

Example 10

cream

A. Paid

Behenyl Alcohol 0.5

12-hydroxystearic acid cholestanol ester 2.0

Squalene 7.0

Jojoba Oil 5.0

Self-emulsifying monoglycerin glycerol 2.5

Polyoxyethylene sorbitan monostearic acid ester 1.5

2-methoxybenzophenone 3.0

Ethylparaben 0.2

Butylparaben 0.1

Propylparaben 0.1

B. Award

Propylene Glycol 5.0

Sodium Editate 0.08

Glycerin 5.0

Bicam (monomori low knight) 3.0

Potassium Hydroxide 0.3

1- (4-benzoyl-3-hydroxyphenyl) glycerolmartotriolether 8.0

Purified water balance

quite

The cream was obtained by Example 7.

Example 11

Powder

A. Paid

Ethanol 8.0

POE (60) glyceryl Monoisostearate 2.0

L-menthol 0.1

Campa 0.1

Methylparaben 0.2

Fragrance quantification

B. Award

Glycerin 3.5

1- (4-benzoylphenyl) glycerolmartotriolether 4.0

Zinc 1.5

Kaolin 0.5

Bentonite 0.3

Sodium hexametaphosphate 0.03

Purified water balance

quite

A lotion was obtained in Example 7.

Example 12

cream

A. Maintenance

Stearic Acid 10.0

Stearyl Alcohol 4.0

Stearic Acid Monoglycerin Ester 8.0

Vitamin E Acetate 0.5

Spices 0.4

Ethylparaben 0.1

Butylparaben 0.1

Propylparaben 0.1

B. Award

Propylene Glycol 8.0

Glycerin 2.0

2-hydroxy-4- (2-maltosyloxyethoxy) benzophenone 8.0

Potassium Hydroxide 0.4

Trisodium Edetate 0.05

Purified water balance

quite

The cream was obtained by Example 7.

Example 13

cream

A. Paid

Cetanol 4.0

Waserine 7.0

Isopropyl myristate 8.0

Squalane 12.0

Dimethylpolysiloxane 3.0

Stearic Acid Monoglycerin Ester 2.2

POE (20) sorbitan monostearate 0.5

Glytile-Stearate 0.1

BHT 0.02

Ethylparaben 0.1

Butylparaben 0.1

Propylparaben 0.1

B. Award

1,2-butylene glycol 7.0

Disodium Edetate 0.07

Phenoxyethanol 0.2

Ascorbic acid phosphate ester magnesium salt 3.0

Polyacrylic acid alkyl ester 1.0

2-hydroxy-4- (2-glyceroylethoxy) benzophenone 8.0

Purified water balance

quite

The cream was obtained by Example 7.

Example 14

latex

A. Paid

Ole Oleit 3.0

Vaseline 7.0

Squalene 5.0

Sorbanthose skioleate ester 0.8

Polyoxyethylene Oleyl Ether (20E.0.) 1.2

Di p-methoxy cinnamic acid glycerin 3.0

Methylparaben 0.1

Spices 0.12

B. Award

Dipropylene Glycol 5.0

Ethanol 3.0

Carboxy Vinyl Polymer 0.17

Sodium Hyaluronate 0.01

Polyacrylic acid alkyl ester 1.0

2,2'-dihydroxy4- (2-maltosyloxyethoxy) benzophenone 4.0

Potassium Hydroxide 0.08

Sodium hexametaphosphate 0.05

Purified water balance

quite

The emulsion was obtained in Example 7.]

Example 15

cream

A. Paid

Behenyl Alcohol 0.5

12-hydroxystearic acid cholestanol ester 2.0

Squalene 7.0

Jojoba Oil 5.0

Self-emulsifying monoglycerin glycerol 2.5

Polyoxyethylene sorbitan monostearic acid ester (20E0) 1.5

2-hydroxy-4-methoxybenzophenone 3.0

Ethylparaben 0.2

Butylparaben 0.1

Propylparaben 0.1

B. Award

Propylene Glycol 5.0

Sodium Edetate 0.08

Glycerin 5.0

(Beckham) montmorillonite 3.0

Potassium Hydroxide 0.3

2,2 ', 4' trihydroxy-4- (2-martosiloxyethoxy) benzophenone 8.0

Purified water balance

quite

The cream was obtained by Example 7.

Example 16

Powdered Cosmetics

A. Paid

Ethanol 8.0

POE (60) glyceryl Monoisostearate 2.0

L-menthol 0.1

Campa 0.1

Methylparaben 0.2

Spices

B. Award

Glycerin 3.5

2-hydroxy-4 (3-maltosiloxybutoxy) benzophenone 4.0

Zinc 1.5

Kaolin 0.5

Bentonite 0.3

Hexametal sodium phosphate 0.03

Purified water balance

quite

A lotion was obtained in Example 7.

As described above, the benzophenone derivative according to the present invention has excellent ultraviolet absorbing ability and polar solvent compatibility.

In addition, it has been found that the external skin preparation blended with the same can be blended with the polar base and exhibits excellent usability.

Claims (11)

Benzophenone derivative represented by following General formula (1), (In the general formula (1), A is a residue obtained by removing one or more hydroxyl groups from a sugar or sugar alcohol, B is a benzophenone group represented by the following general formula (2), (In the general formula (2), R ₁ ~R ₁₀ denotes hydrogen or a hydroxyl group, or alkoxy group or a binder C of the C ₁ ~C _4, is a dog binder C) C corresponds to -ORO- (O is oxygen, R is C _1-4 fatty chain), or 1 mole of glycerin, of which one hydroxyl group is bonded to A and the other hydroxyl group to B, and n is 1 Is an integer greater than or equal to UV absorber, characterized in that it comprises one or two or more benzophenone derivatives according to claim 1. A skin external preparation comprising one or two or more benzophenone derivatives according to claim 1. Benzophenone derivatives represented by the following general formula (3) (In the formula (3), A is a residue obtained by removing one or more hydroxyl groups from a sugar or sugar alcohol, C is equivalent to 1 mole of glycerin, and one of the hydroxyl groups is bonded to A and the other hydroxyl group to B, B is a benzophenone group represented by the following general formula (4), (In the general formula (4), one of R ₁ to R ₉ is C, and the other is hydrogen or a hydroxyl group, an alkyl group, an alkoxyl group.) n is an integer greater than or equal to 1) A ultraviolet absorbent comprising one or two or more benzophenone derivatives according to claim 4. A skin external preparation comprising one or two or more benzophenone derivatives according to claim 4. Benzophenone derivatives represented by the following general formula (7). (In general formula (7), R <_1> , R <_2> is hydrogen or a hydroxyl group, one or more is a hydroxyl group, R <_3> -R <_10> is represented by hydrogen or a hydroxyl group, or the C _1-4 alkoxy group or -OROA. , One is represented by -OROA, A is a residue from which one hydroxyl group is removed from sugar, R is C _1-4 fatty chain) A ultraviolet absorber comprising one or two or more benzophenone derivatives according to claim 7. The external preparation for skin, comprising one or two or more benzophenone derivatives according to claim 7. The benzophenone derivative according to claim 1, wherein -R- is -C ₂ H ₄ -or -C ₃ H _6- . 8. The benzophenone derivative according to claim 7, wherein -R- is -C ₂ H ₄ -or -C ₃ H _6- .